Accelerator



United States Patent O ACCELERATOR Nelson V. Seeger Cuyahoga Falls, andThomas G. Mastin, Akron, Ohio, asslgnors, by mesne assignments, to TheGoodyear Tire & Rubber Company, a corporation of Ohio No Drawing.Continuation of application Serial No.

327,149, December 20, 1952. This application November 20, 1956, SerialNo. 623,287

6 Claims. (Cl. 260-454) This invention relates to a method ofaccelerating the reaction between organic compounds containing reactivehydrogen and compounds containing isocyanate groups. More particularlyit relates to an accelerator for the preparation of syntheticelastomeric polymers. Still more specifically it relates to anaccelerator for the cross-linking reactions between polyisocyanates andelastomeric diisocyanate-modified linear polyesters and polyesteramidessuch as those described in United States Patents 2,625,532; 2,625,531;2,760,953 and copending application Serial Number 305,914, filed August22, 1952, and issued January 15, 1957, as United States Patent2,777,831. These materials which are described in detail below, willhereinafter be referred to as elastomeric diisocyanate-modified linearpolymers.

It has been known to use water and water-liberating compounds, such assalts carrying water of crystallization, in the cure or cross-linking ofelastomeric diisocyanatemodified polymers. Such materials are known toaccelerate the cure of elastomeric dissocyanatemodified polymers.However, the use of such materials is not entirely satisfactory becausethe reactions involved produce CO, gas which causes blisters or bubblesin the cured product. In addition the water reacts with the isocyanateradicals present with the result that more polyisocyanate than thatnormally required must be added to efiect a complete cure.

It is therefore another object of this invention to provide anaccelerator for the cure of elastomeric dissocyanate-modified polymerswhich does not produce the objectionable results obtained by using wateror waterliberating compounds. It is still another object of thisinvention to provide an accelerator for the cure of elastomericdiisocyanatemodified polymers which functions as a catalyst for thecross-linking reaction and which itself does not chemically enter intothe reaction. Other obiects will appear as the description proceeds.

According to the practice of this invention, the elastomericdiisocyanate-modified linear polymer is mixed with the polyisocyanaterequired to etiect a cure of the elastomer and, in addition, theaccelerator referred to above, this being magnesium oxide. Magnesiumoxide catalyzes the reaction between the -NCO groups of thepolyisocyanate and the urethane, urea, or amide linkages present alongthe molecular chains in the modified polymer and thus eflects anaccelerated cure with consequent saving of time and increased productionfrom each unit of equipment. Magnesium oxide appears to be the onlymetallic oxide operable for the purposes of this invention. Other oxideswhich have been tried and found to be inoperative for the purposes ofthis invention are the oxides of lead, zinc, iron, aluminum, calcium,and titanium.

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The amount of magnesium oxide required to catalyze the reaction betweenthe polyisocyanates and the cyanate-modified polymer will, of course,vary depending upon the other ingredients used in compounding the'elastomer. In general, there may be used as little as 0.25

part or as much as parts of the oxide by weight per parts of elastomericpolymer by weight. A preferred range is from 0.50 to 10.0 parts byweight per 100 parts of polymer while a more particularly preferredrange is from 1.0 to 5.0 parts by weight. In general it may be said thatthe degree of acceleration is proportional to the amount of oxide used,since, normally, increased amounts of accelerator will reduce the timerequired to elfect a cure. However, amounts of magnesium oxide in excessof about 10 parts by weight do not seem to have any added effect uponthe rate of cure of the elastomer.

While each class of elastomeric diisocyanate-modified linear polyestershas been fully described in the applications referred to above, thegeneral chemical reactions involved in their preparation have beenillustrated in United States Patent 2,763,628.

The curing or cross-linking of the uncured polymers takes place as theresult of reaction between the -NCO 'groups in the curing agent and thereactive hydrogens in certain groups present in the chain of theextended polymer and certain terminal groups at the ends of thechainextended units. The terminal groups include, of course, hydroxyl,carboxyl, and amino radicals. The groups along the chain include thegroups formed by reaction between an NCO group and a carboxylic,hydroxyl, or amino group, and may be represented as a substituted amidelinkage o H t-i-z'w acarbamic radical o n (O I I-) and a ureyleneradical H 0 H (AFB-is bearing amino groups present, the polyester orpolyester amide having a hydroxyl number from 40 to 100 (a preferredrange is from 50 to 60) and an acid number from 0 to 7; and (2) at leastone diisocyanate selected from the group consisting of 4,4'-diphenyldiisocyanate; 4,4- diphenylene methane diisocyanate; dianisidinediisocyanate; 4,4'-tolidine diisocyanate; 1,5-naphthalene diisocyanate;4,4'-diphenyl ether diisocyanate; and p-phenylene diisocyanate, thediisocyanate being used in an amount ranging from 0.70 to 0.99 (apreferred range is from 0.90 to 0.99) mol per mol of polyester orpolyesteranide.

Second, the reaction product of (l) a polyester or polyesteramideprepared from at least one dibasic carboxylic acid, and at least oneglycol, and/or at least one amino alcohol and/or at least one diamine,the number of hydrogen-bearing amino groups present being in an amountnot to exceed 30% of the total hydroxyl and hydrogen-bearing aminogroups present, the polyester or polyesteramide having a hydroxyl numberfrom 30 to 140 (a preferred range is from 50 to 60) and an acid numberfrom to 12; and (2) at least one tolylene diisocyanate, the diisocyanatebeing used in an amount ranging from 0.85 to 1.10 (a preferred range isfrom 0.90 to 1.00) mols per mol of polyester or polyesteramide.

Third, the reaction product resulting from the reaction of a mixturecomprising (1) a polyester prepared from bifunctional ingredientsincluding at least one dibasic carboxylic acid containing at least threecarbon atoms, and at least one glycol, said polyester having a hydroxylnumber from 30 to 140 (a preferred range is from 50 to 60) and an acidnumber from 0 to 12; (2) at least one bifunctional additive selectedfrom the group consisting of diamines, amino alcohols, dicarboxylicacids, hydroxy carboxylic acids, amino carboxylic acids and the ureas,guanidines and thioureas containing a primary amino group, saidbifunctional additive being used in an amount such that the total numberof --NH, and COOH equivaalents present in said bifunctional reactantshall be from 0.06 to 0.24 equivalent per mol of polyester, and (3) atleast one tolylene diisocyanate, the diisocyanate being used in anamount equal to the sum of from 0.85 mol to 1.10 (a preferred range isfrom 0.90 to 1.00) mols of diisocyanate per mol of polyester plus themolar amount of diisocyanate equivalent to the mols of said bifunctionaladditive used.

Fourth, the reaction product resulting from the reaction of a mixturecomprising (1) a polyester prepared from bifunctional ingredientsincluding at least one dibasic carboxylic acid containing at least threecarbon atoms and at least one glycol, said polyester having a hydroxylnumber between 40 and 100 (a preferred range is from 50 to 60) and anacid number from 0 to 7; (2) at least one bifunctional additive selectedfrom the group consisting of diamines, amino alcohols, dicarboxylicacids, hydroxy carboxylic acids, amino carboxylic acids, and the ureas,guanidines, and thioureas containing a primary amino group, saidbifunctional additive being used in an amount such that the total numberof NH, and COOH equivalents present in said bifunctional reactant shallbe from 0.06 to 0.48 equivalent per mol of polyester, and (3) at leastone diisocyanate selected from the group consisting of 4,4'-diphenyldiisocyanate; 4,4'-diphenylene methane diisocyanate; 4,4'-tolidinediisocyanate; dianisidine diisocyanate; 1,5-naphthalene diisocyanate;4,4- diphenyl ether diisocyanate; and p-phenylene diisocyanate, thediisocyanate being used in an amount equal to the sum of from 0.70 molto 0.99 (a preferred range is from 0.90 to 0.99) mol of diisocyanate permol of polyester plus the molar amount of diisocyanate equivalent to themols of bifunctional additive used.

The amount of polyisocyanate required to cure or crosslink theelastomeric diisocyanate-modified linear polymers is held within certainlimits. Any diisocyanate, polyisocyanate or mixtures of polyisocyanates,or both, may be used. When curing the polymers of the first and secondclasses, enough polyisocyanate must be added to the polymer so that thetotal amount of NCO equivalents, including that added in the formationof the polymer, shall be from 2.80 to 3.20 equivalents per mol ofpolyester or polyesteramide.

When curing the polymers of the third and fourth class, enoughpolyisocyanate must be added to the polymer so that the total amount ofNCO equivalents, including that added in the formation of the polymer,shall be equal to the sum of from 2.80 to 3.20 equivalents per mol ofpolyester or polyesteramide plus twice the molar amount of bifunctionaladditive used in preparing the polymer.

cure the polymer will result in an under-cured product. The use ofgreater amounts is a waste of material with no improved properties inthe cured product and in some cases produces a cured material havingproperties more resinous than rubber-like. If a triisocyanate ortetraisocyanate is used in place of a diisocyanate to effect a cure, notas much material, on a mol basis, need be used, since the curing orcross-linking of the linear molecules depends upon the number of NCOgroups present in the curing agent. For example, if 0.50 mol of adiisocyanate gives a satisfactory cure of a diisocyanate-modifiedpolyester or polyesteramide, the use of approximately 0.25 mol of atetraisocyanate will result in a similar state of cure.

The actual curing of the polymer is accomplished by methods familiar tothose skilled in the art. The time and temperature required to effectthe best cure for any particular polymer will of course vary as is thecase with the curing of conventional natural rubber compounds. The curefor best results should be accomplished by the use of dry heat sinceexposure of the polymer to hot water or steam results in apartialdegeneration of the cured material.

Disclosed in United States Patent 2,763,628 are the reactants used toform some preferred polyesters and polyesteramides which, when preparedand subsequently modified by a diisocyanate and, optionally abifunctional additive in accordance with the appropriate limitationsindicated in the description of the four types of synthetic elastomers,will produce elastomeric products. Also listed in that patent arepreferred diisocyanates combined with preferred polyesters andpolyesteramides employed to form elastomeric diisocyanate-modifiedlinear polymers employed in the practice of this invention.

Of the various elastomeric diisocyanate-modified linear polymersdescribed in the patents referred to above and useful in the practice ofthis invention, the preferred polymers are:

(1) Those prepared from the reaction of a mixture comprising (A) apolyester prepared from at least one dibasic carboxylic acid and atleast one glycol, said polyester having a hydroxyl number from 40 to andan acid number from 0 to 7 and (B) 4,4'-diphenyl diisocyanate used in anamount ranging from 0.90 to 0.99 mol per mol of said polyester.

(2) Those prepared from the reaction of a mixture comprising (A) apolyester prepared from at least one dibasic carboxylic acid and atleast one glycol, said polyester having a hydroxyl number from 30 to andan acid number from 0 to 12 and (B) tolylene diisocyanate used in anamount ranging from 0.90 to 1.00 mol per mol of said polyester.

(3) Those prepared from the reaction of a mixture comprising (A) apolyester prepared from at least one dibasic carboxylic acid containingat least three carbon atoms and at least one glycol, said polyesterhaving a hydroxyl number from 30 to 140 and an acid number from 0 to 12,(B), a diamine used in an amount such that the total number 'of NH,equivalents is from 0.06 to 0.24 equivalent per mol of polyester and (C)tolylene diisocyanate used in an amount equal to the sum of from 0.90 to1.00 mol per mol of polyester plus the molar amount of diisocyanateequivalent to the mols of diamine used.

(4) Those prepared from the reaction of a mixture comprising (A) apolyester prepared from at least one dibasic carboxylic acid containingat least three carbon atoms and at least one glycol, said polyesterhaving a hydroxyl number from 40 to 100 and an acid number from 0 to 7,(B) a diamine used in an amount such that the total number of NH:equivalents is from 0.06 to 0.48 equivalent per mol of polyester and (C)4,4'-diphenyl diisocyanate used in an amount equal to the sum of from0.90 to 0.99 mol per mol of polyester plus the molar amount ofdiisocyanate equivalent to the mole of diamine Smaller amounts ofpolyisocyanate added to 76 used.

5 (5) Those prepared from. the reaction of a mixture comprising (A) apolyester prepared from at leastone dibasic carboxylic acid containingat least one glycol, aid

polyester having a hydroxyl number from 40 to 100 and an acid numberfrom to 7, (B) a diamine used in an I amount such that the total numberof NH, equivalents in the practice of this invention. 'The'seexamplesarerepresentative rather than restrictive 'o'f'the scope of thisinvention.

EXAMPLE 1 Preparation of a typical polyester Adipic acid (3515 parts)was placed in a liter, 3- necked flask fitted with a stirrer,thermo-couple well, gas inlet tube, distilling head, and condenser. Tothe acid were added 1064 parts of ethylene glycol and 869 parts ofpropylene 1,2 glycol. The molar ratio of dibasic acid to glycol is1:1.19. The mixture was heated to 130- 160 C. until most of the waterhad distilled oil. The temperature was then gradually raised to 200 C.,the pressure being gradually reduced to 20 mm. and nitrogen beingbubbled through the melt. After 23% hours a soft white waxy solid wasobtained. Determinations showed the acid number to be 3.5 and thehydroxyl number to be 58.6.

EXAMPLE 2 Preparation of the diisocyanate-modified polymer A quantity ofpolyester was prepared from adipic acid, ethylene glycol, and propylene1,2 glycol according to the general method and in substantially the sameratios as shown in Example 1. This polyester had an acid number of 3.1and a hydroxyl number of 55.6. After heating 2270 parts of thispolyester in a steam-heated Baker- Perkins mixer to 120 C.,4,4'-diphenyl diisocyanate (280.3 parts of 95.7% purity or 0.96 mol permol of polyester) was added. After ten minutes of mixing the hot meltwas poured into a carnauba wax coated tray and baked for 8 hours at 130C. The resulting polymer had excellent processing characteristics on arubber mill. Tests showed the following physical properties-intrinsicviscosity 1.69, percent gel 3.9, plastic flow (1500 p.s.i.- 212 F.) 85seconds per inch, and softening point 186 C.

EXAMPLE 3 Preparation of the diisocyanate-modified polymer A quantity ofpolyester was prepared from adipic acid, ethylene glycol, and propylene1,2 glycol according to the general method and in substantially the sameratios as shown in Example 1. of 3.1 and a hydroxyl number of 55.6.After heating 200 parts of this polyester to 120 C. in an iron kettle,2,4-tolylene diisocyanate (20.11 parts of 99.7% purity or 1.10 mols ofdiisocyante per mol of polyester) was added. After 15 minutes of mixing,the material was poured into a waxed aluminum tray and baked for 8 hoursat 120 C. The resulting polymer had excellent processing characteristicson a rubber mill.

To illustrate the effect of magnesium oxide on the state of cure of theelastomeric diisocyanate-modified polymers, listed below are theformulations and the test results of the elastomers acceleratedaccording to the practice of this invention. Formulations are shown inparts by weight. Tensile strength values are expressed in pounds persquare inch, and the modulus is a measure of the pounds per square inchrequired to elongate the test sample 500%.

This polyester had an acid number.

Formulation. 1 2 8 4 Elastomer 2 Elastomer 8 100 10a 4,4'-dlphenylene2,4-tolylene dt 6. 58 6. 5!

Magnesium Oxide 5. 00

Tensile Strength:

Curedsmlnutes "280 F 1,250 2.450 Cured 10 minutes at 280' F 1,111) 2,450Cured 20 minutes at 280 075 1, 050 C 30 minutes at 280 F 1,400 Cured 15minutes at 240 F 1,125 1.350 Cured 15 minutes at 260 F 1, 225 2, 000Cured 15 minutes at 280 F 900 2, 100 Cured 15 minutes at 300 F 900 1,750 Cured 15 minutes at 320 F 225 600 Modulus 600%:

Cured 5 minutes at 280 F.. 900 1, 200 500 1,025 Cured 10 minutes at 280F. 900 l, 050 375 1, 000 Cured 15 minutes at 280 F 900 1,025 450 825Cured 20 minutes at 280 F 850 a 1, 025 425 760 Cured 30 minutes at 280 F715 1, 050 300 675 Elastomers 2 and 3 shown in the above formulationswere prepared according to Examples 2 and 3 respectively. The elastomer,diisocyanate and magnesium oxide were mixed together on a rubber mill inaccordance with normal procedure in the rubber art.

Analysis'of the test results presented above will indicate twoadvantages attained by the use of magnesium oxide. First, the rate ofcure is accelerated as is evidenced by' the markedly higher tensile andmoduli results in the samples cured for shorter times or at lowertemperatures. It will be noted that the formulations 2 and 4 containingmagnesium oxide produce compounds which achieve their highest tensilestrength when cured for'5 minutes at 280 F. while the same compoundswithout magnesium oxide (formulations 1 and 3) do not achieveequal'tensile strengths even when cured for 30 minutes at 280 F. Thereduction in optimum curing time by use of the magnesium oxide resultsin a reduction in production costs because of the increased curingcapacity available from each unit of equipment.

In addition to accelerating the cure, magnesium oxide has a stabilizingeffect upon the physical propertiesof the formulations as is shown bythe lower reduction in tensile strength and moduli of the magnesiumoxide formulations cured for longer times or at a higher temperature.The stabilization of the physical properties over longer periods ofcuring times and for greater variations in curing temperatures is to bedesired particularly where thick sections are being cured such as in apneumatic tire. Using such heat-stabilized materials it is possible toproduce a product of thick cross section which is cured adequately atthe center and is still not appreciably overcured at the surface-suchover-cure being minimized by the heat-stable compounds whose curedphysical properties remain substantially constant at varying curingtimes and temperatures.

This application is a continuation of our copending application SerialNumber 327,149, filed December 20, 1952, which is a continuation-in-partof Serial Number 248,659, filed September 27, 1951, both now abandoned.

While certain representative embodiments and details have been shown forthe purpose of illustrating the invention, it will be apparent to thoseskilled in this art that various changes and modifications may be madetherein without departing from the spirit or scope of the invention.

We claim:

1. The method of catalyzing the reaction between an elastomericdiisocyanate-modified linear polymer and an organic polyisocyanate whichcomprises conducting said reaction in the presence of magnesium oxide,said elastomeric diisocyanate-modified linear polymer being see lectedfrom the group consisting of (A) the reaction product resulting from thereaction of a mixture comprising (l) a material prepared frombifunctional in; gredients including at least one dicarboxylic acid andmemes:

at least one complementary bifunctional reactant in which the functionalgroups are selected from the class consist ing of the hydroxyl group andthe hydrogen-bearing amino groups, the hydrogen-bearing amino groupsbeing present in an amount not to exceed 7.5% of the total functionalgroups of said complementary bifunctional reactant, said material havinga hydroxyl number irom 40 to 100 and an acid number from to 7, and (2)at least one diisocyanate selected from the group consisting of4,4'-diphenyl diisocyanate; 4,4'-diphenylene methane diisocyanate;dianisidine diisocyanate; 4,4'-tolidine diisocyanate; l,5naphthalenediisocyanate; 4,4"-diphenyl ether diisocyanate, and p-phenylenediisocyanate, the diisocyanate being used in an amount ranging from 0.70to 0.99 mol per mol of said material; (B) the reaction product resultingfrom the reaction of a mixture comprising (3) a material prepared frombifunctional ingredients including at least one dicarboxylic acid and atleast one complementary bifunctional reactant in which the functionalgroups are selected from the class consisting of the hydroxyl group andthe hydrogen-bearing amino groups, the hydrogen-bearing groups beingpresent in an amount not to. exceed 30% of the total functional groupsof said complementary bifunctional reactant, said material having ahydroxyl number from 30 to 140 and an acid number from 0 to 12, and (4)at least one tolylene diisocyanate used in an amount ranging from 0.85to 1.10 mols per mol of said material; (C) the reaction productresulting irom the reaction of a mixture comprising (5) a polyesterprepared from bifunctional ingredients including at least onedicarboxylic acid containing at least three carbon atoms, and at leastone glycol, said polyester having an hydroxyl number from 30 to 140 andan acid number from 0 to 12, (6) at least one bifunctional additiveselected from the group consisting of diamines, amino alcohols,dicarboxylic acids, amino carboxylic acids, hydroxy carboxylic acids andthe ureas, guanidines, and thioureas containing a primary amino group,said bifunctional additive being used in an amount such that the totalnumber of NH; and COOH equivalents present in said bifunctional reactantshall be from 0.06 to 0.24 equivalent per mol of polyester, and (7) atleast one tolylene diisocyanate used in an amount equal to the sum offrom 0.85 mol to 1.10 mols of diisocyanate per mol of polyester plus themolar amount of diisocyanate equivalent to the mols of said bifunctionaladditive used; (D) the reaction product resulting from the reaction of amixture comprising (8) a polyester prepared from bifunctionalingredients including at least one dicarboxylic acid containing at leastthree carbon atoms and at least one glycol, said polyester having ahydroxyl number between 40 and 100 and an acid number from 0 to 7, (9)at least one bifunctional additive selected from the group consisting ofdiamines, amino alcohol, dicarboxylic acids, amino carboxylic acids,bydroxy carboxylic acids, and the ureas, guanidines and thioureascontaining a primary amino group, said bifunctional additive being usedin an amount such that the total number of NH- and COOH equivalentspresent in said bifunctional reactants shall be from 0.06 to 0.48equivalent per mol of polyester, and (10) at least one diisocyanateselected from the group consisting of 4,4- diphenyl diisocyanate;4,4'-diphenylene methane diisocyanate; 4,4'-tolidine diisocyanate;dianisidine diisocyanate; 1,5-naphthalene diisocyanate; 4,4'-diphenylether diisocyanate, and p-phenylene diisocyanate, the diisocyanate beingused in an amount equal to the sum of from 0.70 mol to 0.99 mol ofdiisocyanate per mol of polyester plus the molar amount of diisocyanateequivalent to the mols of bifunctional additive used; (A) and (B) beingreacted with a sufficient amount of at least one organic polyisocyanateto bring the total number of --NCO equivalents present to from 2.80 to3.20 equivalents per mol of said material and (C) and (D) being reactedwith a sufiicient amount of at least one organic polyisocyanate to bringthe total number of NCO equivalents present to the sum of from 2.80 to3.20 equivalents per mol of said polyester plus twice the molar amountof bifunctional additive used in the preparation of said elastomericreaction product.

2. The method defined by claim 1 in which the clastomericdiisocyanate-modified linear polymer results from the reaction of amixture comprising (A) a polyester prepared from at least onedicarboxylic acid and at least one glycol, said polyester having ahydroxyl number from 40 to and an acid number from 0 to 7 and (B) 4,4-diphenyl diisocyanate used in an amount ranging from 0.90 to 0.99 molper mol of said polyester.

3. The method defined by claim 1 in which the clastomericdiisocyanate-modified linear polymer results from the reaction of amixture comprising (A) a polyester prepared from at least onedicarboxylic acid and at least one glycol, said polyester having ahydroxyl number from 30 to and an acid number from 0 to 12 and (B)tolylene diisocyanate used in an amount ranging from 0.90 to 1.00 molper mol of said polyester.

4. The method defined by claim 1 in which the elastomericdiisocyanate-modified linear polymer results from the reaction of amixture comprising (A) a polyester prepared from at least onedicarboxylic acid containing at least three carbon atoms and at leastone glycol, said polyester having a hydroxyl number from 30 to 140 andan acid number from 0 to 12, (B) a diamine used in an amount such thatthe total number of NH equivalents is from 0.06 to 0.24 equivalentpermol of polyester and (C) tolylene diisocyanate used in an amountequal to the sum of from 0.90 to 1.00 mol per mol of polyester plus themolar amount of diisocyanate equivalent to the mols of diamine used.

5. The method defined by claim 1 in which the clastomericdiisocyanate-modified linear polymer results from the reaction of amixture comprising (A) a polyester prepared from at least onedicarboxylic acid containing at least three carbon atoms and at leastone glycol, said polyester having a hydroxyl number from 40 to I00 andan acid number from 0 to 7, (B) a diamine used in an amount such thatthe total number of NH, equivalents is from 0.06 to 0.48 equivalent permol of polyester and (C) 4,4'-diphenyl diisocyanate used in an amountequal to the sum of from 0.90 to 0.99 mol per mol of polyester plus themolar amount of diisocyanate equivalent to the mols of diamine used.

6. The method defined by claim 1 in which the elastomericdiisocyanate-modified linear polymer results from the reaction of amixture comprising (A) a polyester prepared from at least onedicarboxylic acid and at least one glycol, said polyester having ahydroxyl number from 40 to 100 and an acid number from 0 to 7, (B) adiamine used in an amount such that the total number of NH, equivalentsshall be from 0.06 to 0.48 equivalent per mol of polyester and (C)4,4'-tolidine diisocyanate used in an amount equal to the sum of from0.90 to 0.99 mol per mol of polyester plus the molar amount ofdiisocyanate equivalent to the mols of diamine used.

No references cited.

1. THE METHOD OF CATALYZING THE REACTION BETWEEN AN ELASTOMERICDIISOCYANATE-MODIFIED LINEAR POLYMER AND AN ORGANIC POLYISOCYANNATEWHICH COMPRISE CONDUCTING SAID REACTION IN THE PRESENT OF MAGNESIUMOXIDE, SAIS ELASTOMERIC DISOCYANATE-MODIFIED LINEAR POLYMER BEINGSELECTED FROM THE GROUP CONSISTING OF (A) THE REACTION PRODUCT RESULTINGFROM THE REACTION OF A MIXTURE COMPRISING (1) A MATERIAL PREPEARED FROMBIFUNCTIONAL INGREDIENTS INCLUDING AT LEAST ONE DICARBOXYLIC ACID AND ATLEAST ONE COMPLEMENTARY BIFUNCTIONAL REACTION IN WHICH THE FUNCTINALGROUPS ARE SELECTED FROM THE CLASS CONSISTING OF THE HYDROXYL GROUP ANDTHE HYDROGEN-BEARING AMINO GROUPS, THE HYDROGEN-BEARING AMINO GROUPSBEING PRESENT IN AN AMOUNT NOT TO EXCEED 7.5% OF THE TOTAL FUNCTIONALGROUPS OF SAID COMPLEMENTARY BIFUNCTIONAL REACTANT, SAID MATERIAL HAVINGA HYDROXYL NUMBER FROM 40 TO 100 AND AN ACID NUMBER FROM 0 TO 7, AND (2)AT LEAST ONE DIISOCYANATE SELECTED FROM THE GROUP CONSISTING OF4,4''-DIPHENYL DIISOCYANATE; 4,4''-DIPHENYLENE METHANE DIISOCYANATE;DIANISIDANE DIISOCYANATE; 4,4''-TOLIDEINE DIISOCYANATE; 1,5-NAPHTHALENEDIISOCYANATE; 4,4''-DIPHENYL ETHER DIISOCYANATE, AND P-PHENYLENEDIISOCYANATE,THE DISSOCYANATE BEING USED IN AN AMOUNT RANGING FROM 0.70TO 0.99 MOL PER MOL OF SAID MATERIAL;(B) THE REACTION PRODUCT RESULTINGFROM THE REACTION OF A MIXTURE COMPRISING (3) A MATERIAL PREPARED FROMBIFUNCTIONAL INGREDIENTS INCLUDING AT LEAST ONE DIACARBOXYLID ACID ANDAT LEAST ONE COMPLEMENTARY BIFUNCTIONAL REACTANT IN WHICH THE FUNCTIONALGROUPS ARE SELECTED FROM THE CLASS CONSISTING OF THE HYDROXYL GROUP ANDTHE HYDROGEN-BEARING AMINO GROUPS, THE HYDROGEN-BEARING GROUPS BEINGPRESENT IN AN AMOUNT NOT TO EXCEED 30% OF THE TOTAL FUNCTIONAL GROUPS OFSAID COMPLEMENTARY BIFUNCTIONAL REACTANT, SAID MATERIAL HAVING AHYDROXYL NUMBER FROM 30 TO 140 AND AN ACID NUMBER FROM 0 TO 12, AND (4)AT LEAST ONE TOLYLENE DISSOCYANATE USED IN AN AMOUNT RANGING FROM 0.85TO 1.10 MOLS PER MOL OF SAID MATERIAL; (C) THE REACTION PRODUCERESULTING FROM THE THE REACTION OF A MIXTURE COMPRISING (5) A POLYESTERPREPEARED FROM BIFUNCTIONAL INGREDIENTS INCLUDING AT LEAST ONEDICARBOXYLIC ACID CONTAINING AT LEAST THREE CARBON ATOMS, AND AT LEASTONE GLYCOL,SAID POLYESTER HAVING AN HYDROXYL NUMBER FROM 30 TO 140 ANDAN ACID NUMBER FROM 0 TO 12, (6) AT LEAST ONE BIFUNCTIONAL ADDITIVESELECTED FROM THE GROUP CONSISTING OF DIAMINES, AMINO ALCOHOLS,DICARBOXYLIC ACIDS AMINO CARBOXYLIC ACIDS, HYDROXY CARBOXYLIC ACIDS ANDTHE UREAS, GUANIDINES, AND THIOUREAS CONTAINING A PRIMARY AMINO GROUP,SAID BIFFUNCTIONAL ADDITIVE BEING USED IN AN AMOUNT SUCH THAT THE TOTALNUMBER OF-NH2 AND-COOH EQUIVALENTS PRESENT IN SAID BIFUNCTIONAL REACTANTSHALL BE FORMED 0.06 TO 0.24 EQUIVALERNT PER MOL OF POLYESTER, AND (7)AT LEAST ONE TOLYLENE DISSOCYANATE USED IN AN AMOUNT EQUAL TO THE SUM OFFROM 0.85 MOLE TO 1.10 MOLS OF DISOCYANATE MOL OF POLYESTER PLUS THEMOLAR AMOUNT OF DISSOCYANATE EQUIVALENT TO THE MOL OF SAID BIFUNCTIONALADDITIVE USED; (D) THE REACTION PRODUCE RESULTING FROM THE REACTION OF AMIXTURE COMPRISING (8) A POLYESTER PREPARED FROM BIFUNCTIONALINGREDIENTS INCLUDCARBON ATOMS AND AT LEAST ONE GLYCOL, SAID POLYESTERHAVING A HYDROXYL NUMBER BETWEEN 40 AND 100 AND AN ACID NUMBER FROM 0 TO7, (9) AT LEAST ONE BIFUNCTIONAL ADDITIVE SELECTED FROM THE GROUPECONSISTING OF DIAMINES AMINO ALCOHOL, DICARBOXYLIC ACIDS, AMINOCARBOXYLIC ACIDS, HYDROXY CARBOXYLIC ACIDS, AND THE UREAS, GUANIDINESAND THIOUREAS CONTAINING A PRIMARY AMINO GROUP, SAID BIFUNCTIONALADDITIVE BEING USED IN AN AMOUNT SUCH THAT THE TOTAL NUMBER OF-NH2 AND-COOH EQUIVALENT PRESENT IN SAID BIFUNCTIONAL REACTANTS SHALL BE FORMED0.06 TO 0.48 EQUIVALENT PER MOL OF POLYESTER, AND (10) AT LEAST ONEDISSOCYANATE SELECTED FROM THE GROUPE CONSISTING OF 4,4''DIPHENYLDISSOCYANATE; 4,4''-DIPHENYLENE METHANE DISSOCYANATE; 4,4''-TOLIDINEDISSOCYANATE; DIANISDINE DIISOCYANATE; 1,5-NAPHTHALENE DISSOCYANIATE;4,4''-DIPHENYL ETHER DISSOCYANATE, AND P-PHENYLENE DIISOCYANATE, THEDIISOCYANTE BEING USED IN AN AMOUNT EQUAL TO THE SUM OF FROM 0.70 MOL TO0.99 MOL OF DISSOCYANATE,PER MOL OF POLYESTER PLUS THE MOLAR AMOUNT OFDIISOCYANATE EQUIVALENT TO THE MOL OF BIFUNCTIONAL ADDITIVE USED; (A)AND (B) BEING REACTED WITH A SUFFICENT AMOUNT OF AT LEAST ONE ORGANICPOLYISOCYANATE TO BRING THE TOTAL NUMBER OF -NCO EQUIVALENT PRESENT TOFORM 2.80 TO 3.20 EQUIVALENTS PER MOL OF SAID MATERIAL AND (C) AND (D)BEING REACTED WITH SUFFICENT AMOUNT OF AT LEAST ONE ORGANICPOLYISCOYANATE TO BRING THE TOTAL NUMBER OF -NCO EQUIVALENT PRESENT TOTHE SUM OF FROM 2.80 TO 3.20 EQUIVELENT PER MOL OF SAID POLYESTER PLUSTHE MOLAR AMOUNT OF BIFUNCTIONAL ADDITIVE USED IN THE PREPARATION OFSAID ELASTOMERIC REACTION PRODUCT.